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WO2011101342A1 - Traitement d'eaux usées contenant des acides fluorés ou leurs sels - Google Patents

Traitement d'eaux usées contenant des acides fluorés ou leurs sels Download PDF

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Publication number
WO2011101342A1
WO2011101342A1 PCT/EP2011/052204 EP2011052204W WO2011101342A1 WO 2011101342 A1 WO2011101342 A1 WO 2011101342A1 EP 2011052204 W EP2011052204 W EP 2011052204W WO 2011101342 A1 WO2011101342 A1 WO 2011101342A1
Authority
WO
WIPO (PCT)
Prior art keywords
acids
salts
dilute aqueous
fluorinated
anion
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/EP2011/052204
Other languages
German (de)
English (en)
Inventor
Eike Gabel
Helmut Lahr
Thomas Gruber
Stefan Neumann
Uwe BÖGER
Axel Boddenberg
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Lanxess Deutschland GmbH
Original Assignee
Lanxess Deutschland GmbH
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Lanxess Deutschland GmbH filed Critical Lanxess Deutschland GmbH
Priority to JP2012553290A priority Critical patent/JP2013519517A/ja
Priority to US13/577,325 priority patent/US20130168319A1/en
Priority to EP11703016A priority patent/EP2536503A1/fr
Priority to CN2011800101384A priority patent/CN102762304A/zh
Publication of WO2011101342A1 publication Critical patent/WO2011101342A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/42—Treatment of water, waste water, or sewage by ion-exchange
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
    • C07C51/42—Separation; Purification; Stabilisation; Use of additives
    • C07C51/47—Separation; Purification; Stabilisation; Use of additives by solid-liquid treatment; by chemisorption
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J41/00—Anion exchange; Use of material as anion exchangers; Treatment of material for improving the anion exchange properties
    • B01J41/04—Processes using organic exchangers
    • B01J41/05—Processes using organic exchangers in the strongly basic form
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J41/00—Anion exchange; Use of material as anion exchangers; Treatment of material for improving the anion exchange properties
    • B01J41/04—Processes using organic exchangers
    • B01J41/07—Processes using organic exchangers in the weakly basic form
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J47/00—Ion-exchange processes in general; Apparatus therefor
    • B01J47/016—Modification or after-treatment of ion-exchangers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J49/00—Regeneration or reactivation of ion-exchangers; Apparatus therefor
    • B01J49/50—Regeneration or reactivation of ion-exchangers; Apparatus therefor characterised by the regeneration reagents
    • B01J49/57—Regeneration or reactivation of ion-exchangers; Apparatus therefor characterised by the regeneration reagents for anionic exchangers
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/42—Treatment of water, waste water, or sewage by ion-exchange
    • C02F2001/422—Treatment of water, waste water, or sewage by ion-exchange using anionic exchangers

Definitions

  • the invention relates to a process for the separation of fluorinated acids, in particular perfluorocarboxylic acids and perfluorosulfonic acids or their salts from dilute aqueous solutions with the aid of anion exchangers.
  • Fluorinated acids such as in particular perfluorocarboxylic acids (PFCA) and perfluorosulfonic acids (PFSA)
  • PFCA perfluorocarboxylic acids
  • PFSA perfluorosulfonic acids
  • US Pat. No. 5,442,097 discloses a process for the recovery of fluorinated carboxylic acids in utilizable form from contaminated starting materials, wherein the fluorinated carboxylic acid is released from these materials in aqueous solutions with a sufficiently strong acid if necessary, reacted with a suitable alcohol and the resulting Distilled off ester.
  • the starting material used here can be a polymerization liquor, in particular from the so-called emulsion polymerization, in which fluoropolymers in the form of colloidal particles are prepared in the presence of relatively high amounts of fluorine-containing carboxylic acids as surfactants.
  • the recovery process is said to have worked well, but requires a relatively high concentration of fluorinated carboxylic acid in the starting material.
  • DE 198 24 614 A discloses a process in which initially finely divided solids and / or solids convertible from the wastewater are removed, then fluorinated acids are bound to an anion exchange resin and from this the fluorinated acids are eluted.
  • a disadvantage of the aforementioned method is that the selectivity of the ion exchanger and thus the efficiency of the separation is insufficient. It was therefore an object to provide a process that allows the most complete possible removal of fluorinated acids from dilute aqueous solutions.
  • a process has now been found for the separation of fluorinated acids or their salts from their dilute aqueous solutions by contacting the abovementioned solutions with an anion exchanger, which is characterized in that the anion exchangers used are those which are present at least partially in the fluoride form.
  • dilute aqueous solution in the context of the invention means a liquid medium having a solids content of less than 5 wt .-%, preferably less than 1 wt .-% and particularly preferably less than 0.05 wt .-%, which is at least 80 Wt .-%, preferably at least 90 wt .-% water and at least one fluorinated acid or at least one salt of a fluorinated acid, wherein the total amount of fluorinated acid or salts of fluorinated acids 0.0005 to 5 wt .-%, preferably 0.0005 to 2 wt .-%, more preferably 0.005 to 1 wt .-% and most preferably 0.01 to 0.5 wt .-% is.
  • Fluorinated acids within the meaning of the invention are those which have 1 to 30 carbon atoms and at least one fluorine atom and, under standard conditions, have a pKa of 6.0 or less, preferably of 4.0 or less, more preferably of 3.2 or less.
  • One or more, preferably one acid group may be present, wherein the indication of the pKs value in the case of polybasic acids refers to the respectively first deprotonation stage.
  • Preferred fluorinated acids in the context of the invention are perfluorocarboxylic acids of the formula (I) and perfluorosulfonic acids of the formula (II) F- (CF 2 ) n COOH (I)
  • n and m are each an integer from 1 to 24, preferably 1 to 12 and particularly preferably 4 to 8 and very particularly preferably 4.
  • a salt of a fluorinated acid is meant a compound in which the acid proton is replaced by another cation, such as a metal cation or ammonium ion.
  • Anionic exchangers which are at least partially in fluoride form are those to which fluoride anions are bound via ionic interactions.
  • Suitable anion exchangers comprise strongly basic and weakly basic anion exchangers, whereby strongly basic anion exchangers are to be understood in particular as those which contain quaternary ammonium ions and those which are weakly basic and which contain as structural element primary, secondary or tertiary amine groups or their corresponding ammonium ions.
  • Preferred strongly basic anion exchangers are those which have the structural element of the formula (III)
  • R, R and R are each independently of the other Ci-Ci2-alkyl, which is either not, one or more times by hydroxy or Ci-C alkoxy shimmerer or two of the radicals together are C 2 -C 12 -alkylene, which may be monosubstituted or polysubstituted by hydroxy or C 1 -C 4 -alkoxy and
  • X is an anion which, in a preferred process form, is derived from the
  • Preferred weakly basic Aniontaiischer are those which have the structural element of the formula (IV) or the structural element of the formula (V) or structural elements of the formulas (IV) and (V) have -N + (R 4 5 R 6 ) X " (IV in which
  • R 4 , R 5 and R 6 are each independently of one another hydrogen or C 1 -C 12 -alkyl which may either not be monosubstituted, mono- or polysubstituted by hydroxy or C 1 -C 4 -alkoxy, or, if two of the radicals R 4 , R 5 and R 6 are not hydrogen, these radicals together are C 2 -C 12 -alkylene, which may be monosubstituted or polysubstituted by hydroxy or C 4 -C 4 -alkoxy and
  • At least one, preferably one or two, more preferably one of the radicals R 4 , R 5 and R 6 is hydrogen and X- is an anion which in a preferred process form from the group fluoride,
  • Chloride, bromide, hydroxide, nitrate, hydrogen sulfate and sulfate is selected
  • Alkoxy can be further substituted, or, if two of the radicals R 7 and R 8 are not hydrogen, these radicals together represent C 2 -C [ 2 -alkylene, which may be monosubstituted or polysubstituted by hydroxy or Ci-Cs-alkoxy ,
  • suitable ion exchangers also include those which have the structural elements of the formulas (III) and (IV) and / or (V).
  • Weakly basic ion exchangers are preferred, those which are even more preferred having the structural element of the formulas (IV) and / or (V).
  • a particularly preferred anion exchanger is Lewatit® MP 62 from Lanxess Deutschland GmbH, a weakly basic, macroporous anion exchanger with tertiary amino groups.
  • the anion exchanger is at least partially in fluoride form, i. fluoride anions are bound to the anion exchangers via ionic interactions.
  • this is accomplished by contacting A) the anion exchangers used with salts containing hydrogen fluoride and / or fluoride anions prior to contacting with the dilute aqueous solutions of the fluorinated acids or their salts such that after contacting at least a portion, preferably at least 80%, more preferably at least 90%, of the anions bound by ionic interactions are fluoride anions and / or
  • the dilute aqueous solutions continue to contain hydrogen fluoride and / or fluoride anions or are added prior to contacting with the anion exchanger with hydrogen fluoride and / or fluoride anion-containing salts.
  • the content of the dilute aqueous solution of fluorinated acids or their salts is preferably 0.05 to 10% by weight of hydrogen fluoride or fluoride anion-containing salts, based on hydrogen fluoride.
  • the pH of the dilute aqueous solution of fluorinated acids or their salts is from 1.0 to 10.0, preferably 2.0 to 10.0, more preferably 3.0 to 9.0, and most preferably 3 , 0 to 8.0 each at standard conditions ,.
  • the pH is preferably 3.5 to 7.5, preferably 5.5 to 7.0 and more preferably 6.0 to 6.8 under standard conditions.
  • the contacting of the dilute aqueous solutions of fluorinated acids or their salts with the anion exchanger can be carried out in a conventional manner, for example, the anion exchangers can be arranged in conventional apparatus such as tubes or columns, which are flowed through by the dilute aqueous solutions.
  • the effluent remaining after contacting the dilute aqueous solutions of fluorinated acids or their salts with the anion exchanger typically has a significantly lower content of fluorinated acids or their salts than before contacting, the process preferably being controlled so that at least 80 wt. -% of the present in the dilute aqueous solutions used fluorinated acids or their salts are bound by the anion exchanger, preferably 90 wt .-%.
  • anion exchanger is regenerated or replaced after flowing through or contacting a certain amount of dilute aqueous solution.
  • the capacity of the anion exchanger for fluorinated acids or their salts depends inter alia on the type of anion exchanger chosen and the type and content of the dilute aqueous solutions used in fluorinated acids or their salts. However, this can be determined in simple preliminary tests by a person skilled in a conventional manner
  • the effluent obtained after contacting with the anion exchanger contains hydrogen fluoride and / or fluoride anions, which can preferably be at least partially precipitated in a further step by adding calcium salts in the form of calcium fluoride.
  • the wastewater may be contacted with conventional adsorbents, such as activated carbon, to remove any residual fluorinated acids or their salts.
  • adsorbents such as activated carbon
  • the invention further includes a method of conditioning anion exchange by contacting it with an acid, wherein the acid is hydrofluoric acid, and the use of hydrofluoric acid to condition anion exchangers.
  • the above-mentioned preferred ranges for anion exchangers apply in the same way.
  • the content of hydrogen fluoride in the hydrofluoric acid for conditioning for example, 0.1 to 38 wt .-%, preferably 1 to 25 and particularly preferably 2.5 to 10 wt .-% amount.
  • the eluate typically contains fluorinated acids or their salts in an enriched form compared to the dilute aqueous solutions, as well as hydrogen fluoride.
  • the enrichment can be, for example, 10 to 200 times, preferably 20 to 50 times, based on the content of the fluorinated acids and their salts.
  • the fluorinated acids or their salts can optionally be extracted after esterification, for example, with an organic solvent or the enriched eluate be disposed of, for example by wastewater incineration.
  • the inventive method is particularly suitable for dilute aqueous solutions containing fluorinated acids and / or their salts, which originate from the production of perfluorosulfonic by electrofluorination.
  • Such electrofluorinations for example for the production of perfluorosulfonic acids, typically produce dilute aqueous solutions of perfluorosulfonic acids as effluents, which may furthermore contain perfluorocarboxylic acids, for example from oxidative side reactions and radicals of the hydrogen fluoride used, by exhaust gas and product purification.
  • the aforementioned dilute aqueous solutions may further contain sulfonyl fluoride and typically have a pH of 0 to 3.5.
  • the hydrolysis of sulfonyl fluoride and optionally separation of hydrogen fluoride it is preferred to first adjust the pH of the dilute aqueous solutions to 10 to 14, preferably II to 13, by addition of basic salts, to separate any precipitated salts and to obtain the dilute aqueous solution obtained to adjust to a pH as defined above.
  • the separation of precipitated calcium fluoride can be carried out in a manner known per se, for example by filtration, if necessary with a filtration aid, by decantation, centrifugation or sedimentation.
  • Basic salts are, for example, carbonates and hydroxides of sodium, potassium and calcium, or mixtures thereof.
  • the advantage of the invention is seen in the superior separation of fluorinated acids or their salts from dilute aqueous solutions compared to the prior art.
  • Example 1 Sample preparation Effluents from the production of perfiuorbutanesulfonic acid were collected and hydrofluoric acid adjusted to a pH of 6.2.
  • the dilute aqueous solution from Example 1 was passed over the anion exchanger at a rate of 4 bed volumes (ie 400 ml) per hour at a linear rate and the concentration of perfiuorbutanesulphonic acid or its salts (PFBS) or the concentration of perfluorobutyric acid or their salts (PFBA) at intervals of 2.5 hours by HPLC-MS.
  • PFBS perfiuorbutanesulphonic acid or its salts
  • PFBA perfluorobutyric acid or their salts
  • PFBS perfiuorbutanesulfonic acid or its salts
  • PFBA perfluorobutanoic acid or its salts
  • Example 3 Elution The faeladene according to Example 2 anion exchangers were regenerated over a period of 30 minutes with a total of 200 ml of a 7 wt .-% sodium hydroxide solution and then washed the anion exchanger over a period of 60 minutes with a total of 400 ml of water, the steps each with a linear rate were made. The eluates were combined and disposed of.
  • the anion exchanger regenerated according to Example 3 was conditioned with 3 bed volumes (i.e., 300 ml) of a 4% by weight hydrofluoric acid solution at linear speed over a period of 45 minutes, analogously to Example 2, and used again for an adsorption test according to Example 3.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Hydrology & Water Resources (AREA)
  • Environmental & Geological Engineering (AREA)
  • Water Supply & Treatment (AREA)
  • Treatment Of Water By Ion Exchange (AREA)
  • Removal Of Specific Substances (AREA)
  • Solid-Sorbent Or Filter-Aiding Compositions (AREA)

Abstract

L'invention concerne un procédé de séparation d'acides fluorés, notamment d'acides perfluorocarboxyliques et d'acides perfluorosulfoniques ou leurs sels de solutions aqueuses diluées à l'aide d'échangeurs d'anions.
PCT/EP2011/052204 2010-02-18 2011-02-15 Traitement d'eaux usées contenant des acides fluorés ou leurs sels Ceased WO2011101342A1 (fr)

Priority Applications (4)

Application Number Priority Date Filing Date Title
JP2012553290A JP2013519517A (ja) 2010-02-18 2011-02-15 フッ素化酸またはそれらの塩を含む廃水の処理
US13/577,325 US20130168319A1 (en) 2010-02-18 2011-02-15 Treatment of waste water containing fluorinated acids or the salts thereof
EP11703016A EP2536503A1 (fr) 2010-02-18 2011-02-15 Traitement d'eaux usées contenant des acides fluorés ou leurs sels
CN2011800101384A CN102762304A (zh) 2010-02-18 2011-02-15 含氟代酸或其盐的废水的处理

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
EP10001656.7 2010-02-18
EP10001656 2010-02-18

Publications (1)

Publication Number Publication Date
WO2011101342A1 true WO2011101342A1 (fr) 2011-08-25

Family

ID=42235893

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/EP2011/052204 Ceased WO2011101342A1 (fr) 2010-02-18 2011-02-15 Traitement d'eaux usées contenant des acides fluorés ou leurs sels

Country Status (7)

Country Link
US (1) US20130168319A1 (fr)
EP (1) EP2536503A1 (fr)
JP (1) JP2013519517A (fr)
CN (1) CN102762304A (fr)
AR (1) AR080193A1 (fr)
TW (1) TW201141612A (fr)
WO (1) WO2011101342A1 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US12410071B1 (en) 2020-10-19 2025-09-09 Wm Intellectual Property Holdings, L.L.C. System and method for removal of PFAS and other emerging contaminant micro-constituents from landfill leachate and other impacted liquids

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPWO2023063339A1 (fr) * 2021-10-13 2023-04-20

Citations (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE2044986A1 (fr) 1969-09-12 1971-03-25
DE2653229A1 (de) * 1976-11-23 1978-05-24 Gnii Cvetnych Metallov Gincvet Verfahren zur reinigung von fluorwasserstoffsaeure
US4282162A (en) 1979-02-02 1981-08-04 Hoechst Aktiengesellschaft Recovery of fluorinated emulsifying acids from basic anion exchangers
US5442097A (en) 1993-06-02 1995-08-15 Hoechst Aktiengesellschaft Process for the recovery of fluorinated carboxylic acids
EP0774442A1 (fr) * 1995-11-15 1997-05-21 Mitsubishi Gas Chemical Company, Inc. Procédé de production d'une solution aqueuse purifiée de peroxyde d'hydrogène
DE19824614A1 (de) 1998-06-02 1999-12-09 Dyneon Gmbh Verfahren zur Rückgewinnung von fluorierten Alkansäuren aus Abwässern
WO2004078836A1 (fr) * 2003-02-28 2004-09-16 3M Innovative Properties Company Dispersion de fluoropolymere contenant peu ou pas de surfactant fluore de faible poids moleculaire
US20050113507A1 (en) * 1998-12-11 2005-05-26 3M Innovative Properties Company Aqueous dispersions of fluoropolymers
US20060037913A1 (en) * 2004-08-20 2006-02-23 Resintech Incorporated Modified anion exchange materials with metal inside the materials, method of making same and method of removing and recovering metals from solutions
US20090221726A1 (en) * 2006-11-24 2009-09-03 Asahi Glass Company, Limited Process for producing aqueous fluorinated polymer dispersion having reduced content of fluorinated emulsifier

Family Cites Families (5)

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Publication number Priority date Publication date Assignee Title
JPS57144040A (en) * 1981-02-27 1982-09-06 Japan Organo Co Ltd Removal method for silicic acid in water
DE19933696A1 (de) * 1999-07-17 2001-01-18 Dyneon Gmbh Verfahren zur Rückgewinnung fluorierter Emulgatoren aus wässrigen Phasen
DE19953285A1 (de) * 1999-11-05 2001-05-10 Dyneon Gmbh Verfahren zur Rückgewinnung fluorierter Emulgatoren
JP2002059160A (ja) * 2000-08-11 2002-02-26 Daikin Ind Ltd 含フッ素陰イオン系界面活性剤の分離方法
US7795332B2 (en) * 2005-07-15 2010-09-14 3M Innovative Properties Company Method of removing fluorinated carboxylic acid from aqueous liquid

Patent Citations (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE2044986A1 (fr) 1969-09-12 1971-03-25
DE2653229A1 (de) * 1976-11-23 1978-05-24 Gnii Cvetnych Metallov Gincvet Verfahren zur reinigung von fluorwasserstoffsaeure
US4282162A (en) 1979-02-02 1981-08-04 Hoechst Aktiengesellschaft Recovery of fluorinated emulsifying acids from basic anion exchangers
US5442097A (en) 1993-06-02 1995-08-15 Hoechst Aktiengesellschaft Process for the recovery of fluorinated carboxylic acids
EP0774442A1 (fr) * 1995-11-15 1997-05-21 Mitsubishi Gas Chemical Company, Inc. Procédé de production d'une solution aqueuse purifiée de peroxyde d'hydrogène
DE19824614A1 (de) 1998-06-02 1999-12-09 Dyneon Gmbh Verfahren zur Rückgewinnung von fluorierten Alkansäuren aus Abwässern
US20050113507A1 (en) * 1998-12-11 2005-05-26 3M Innovative Properties Company Aqueous dispersions of fluoropolymers
WO2004078836A1 (fr) * 2003-02-28 2004-09-16 3M Innovative Properties Company Dispersion de fluoropolymere contenant peu ou pas de surfactant fluore de faible poids moleculaire
US20060037913A1 (en) * 2004-08-20 2006-02-23 Resintech Incorporated Modified anion exchange materials with metal inside the materials, method of making same and method of removing and recovering metals from solutions
US20090221726A1 (en) * 2006-11-24 2009-09-03 Asahi Glass Company, Limited Process for producing aqueous fluorinated polymer dispersion having reduced content of fluorinated emulsifier

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US12410071B1 (en) 2020-10-19 2025-09-09 Wm Intellectual Property Holdings, L.L.C. System and method for removal of PFAS and other emerging contaminant micro-constituents from landfill leachate and other impacted liquids

Also Published As

Publication number Publication date
CN102762304A (zh) 2012-10-31
US20130168319A1 (en) 2013-07-04
AR080193A1 (es) 2012-03-21
TW201141612A (en) 2011-12-01
JP2013519517A (ja) 2013-05-30
EP2536503A1 (fr) 2012-12-26

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